Self-extinguishing molding material based on propylene polymers



. is P Y O F 3,419,518 Patented Dec. 31, 1968 ganic compounds which contain 70 to 80% by weight of 3,419,518 aliphatically combined bromine and w ose oiling point SELF-EXTINGUISHING MOLDING MATERIAL BASED ON PROPYLENE POLYMERS Dieter Mahling, Heinz Mueller-Tamm, and Huhertus bromination products of araliphatic compounds bearing ,one or more bromine atoms on the aliphatic radical. Or-

at atmospheric pressure is at least 200 C. are particularly suitable. Brominated hydrocarbons, brominated amides and brominafed a l ohols are preferred. Examples of 3: gfig i g fg gggx i: these w are very suitable are linear and branched F a assignors to Bmfische m & s d ir ik brominated alkanes having six to twelve carbon atoms, Aktiengesellschaft, Ludwigshafen (-Rhine), Germany brominated araliphatic hydrocarbons having ten to twenty No Drawing. Filed May 31, 1963, Ser. No. 284,320 carbon atoms and one benzene nucleus free from bro- Claims priority, application Germany lune 8, 1962, 10 mine atoms, brominated c cloalkanes ing six to l B 67,609 twelve carbon atoms in their rin s, brominated a 1p to g 4 Clamlsamiderofcarb'oxy or s containing two to five carbon 5 atoms in the acid radical, and brominated aliphatic alcog g relates a selfiextmgu 2 3 hols having three to six carbon atoms. Linear araliphatic maienal i popy ene 9 8 d S hydrocarbons which contain sixteen carbon atoms, one mom an an i i i c h benzene nucleus free from bromine atoms and six to P F 9 i Fame ary p0 ypropye eight aliphatically combined bromine atoms, especially gaining increasing importance as raw materials for the phenylhexabromodecane and bwminated 0 C10 anes 1; manufacture of sheets, fibers, hollow articles and other containin Si carbon m 6 rings and 5' molded objects. Their ready flammability is, however, a -W eight m e i disadvanta e in their application particularly to some ma particularly suitable, and also brommated alcohols defields. of i q engmeefnig and cwll engmeermg and rived from butene-2, particularly bromobutenediols which also mmmg 1 fgp i 1 B d o 1 contain at least two bromine atoms and whose double It 15 known t mo ena age on?! a linkage is in 2-position. Examples of particularly suitable polymers and tnoxlde Whlch t i c bromine compounds are: 1,2,3,4-tetra romocyclooctane, nated paraffins, substituted 2,4,6-tr1oromoan1l1nes or phe- 1 2 5 6 tetrabromocycloocmne 1 2 5 6 nols or phenol ethers substituted on the benzene nucleus 1 phenyl 1 2 4 1 with bromine atoms is self-extinguishing. In these prior fidibmmotinilj yclohexane L iq the tatal aliwunt g tri-(a,,B-dibromopropionyl)-trimethylene triamine and y moxlde r a ogen 9 9 mus as m e methylene-bis(1,2-dibromo-l-methylpropionamide). relatively large 1f the self-extinguishing properties are to flomopolymers and copolymers of propylene having satisfy the requirements in practice. The amounts required molecular Weights (measured according o Uberreiter for this purpose are usually more than 15% by weight. Makromolekulare Chemie 8 (1952) 2148) of When such large amounts of flame-retardant substances of tween about 100 000 and 2 000 000 suitable p w the said type are added, however, amoldmg material 18 obfine polymers. Tllese p y 6 pg py y be Ob tamed Whose mechanical d elecmcalhpmpfiirfues are tained by well-known and conventional methods particconsiderably deteriorated. oreover, suc mo mg maa terial often has other disadvantages. For exanfiple moldigg' gg gpgifi i gl gggfigis' g g i g fig gg zf i g; gilfiziiealwgciailltaraiiggs03313223221331; gitgnmoilg :22; 4O particular interest because of its good properties. The rial which contains phenols substituted on the benzene gg gg gfi 225325353 5 if gz g g z g x gggg gf i g g zfi gg 1 5 3223; gag Copolymers suitable for use in the molding material are material based on propylene polymers, particularly based $2 gzi gi ggg ggg z 5 2; 3: 383 g sg zg on polypropylene which ggfi ig saturated Polyrncrizable compounds such as ethylene t i i ii v inii a if w gifvfii moiiiiri; matzri 11525 :n bum-L vinyl acetate, vinyl Propionate styrene and 1, p01 propylene which has no disadreeable Odor also acrylic and methacrylic esters of aliphatic alcohols. 1 a have found that molding nfaterial based propyl In addition to the flame-retardant additives accordtilng r to this invention, the moldin material ma contain ot er 5 ene polymers Fmtlmonymox-lde and orgamc bron-nne prior art flame-retardant a dditives stab ilizing agents 2 Whml-1 Contains Wlth reference t9 g vfvelglzt lubricants dyes fillers antistatic compounds and in 3 :3 :53g ggg ig 2; 22; gi fi amounts up to 30% by weight with reference to the cau-l niwhich contains 45 my93% g a amount of polypropylene, other solid plastics which are g i g 6 the weight of the organic i g of 5 miscible with polypropylene, such as polyisobutylene or polyethylene. Examples of such additives or stabilizing 'gf g i ggg g i gg g zgi g g gig z ig agents are: thioesters, such as dilauryl thiodipropionate, and oroanic bron'line compound together bisphenols, aromatic sulfides and disulfides, organic phosphites, benzophenone derivatives, thiazole derivatives, from 2 to by Wiflght (Wlth ref-wince to the weight epoxides, stearates, salicylates, carbon black, and comth? [Folding maienal) have pg'rtlcularly-good Self-explex-forming substances such as pentaerythritol and altmgul-shmg propertles' moldmg matem-fl greferably kali salts of tartaric acid and of ethylene diamine tetraf to 22 a 2 2: if'ggg g z g g ia ai cetic acid. Preferred additives are amounts of up to 50% o finance to the ht 6 th by weight (with reference to the weight of compound gfg z sii f l W e g e containing aliphtatically combined bromine) of chloriz leg of ('"ganic Compounds containing bromine nated polyisobutylene and/or chlorinated parafiins having in aliphgtic combination are bromination products of a chlorine content of 50 to 80% by weight (with refer' linear, branched or cyclic aliphatic compounds such as to the Welght 9 the chlormatedhfiompounfl) and/Or hydrocarbons, carboxylic acids, carboxylic amides, carp y b i d sl g go 10h l f hl boxylic esters, nitriles, alcohols and amines, and also three enlene 11116 61 an to v y Welg to rine and/or bromine attached to the benzene nuclei. Examples of polynuclear aromatic compounds from which the last-mentioned aromatic halogen compounds may be derived are diphenyl ether, diphenylene oxide, diphenyl,

naphthalene and phenanthrene and also their alkyl Substitution products.

It is surprising that the molding material according to this invention is particularly self-extinguishing because molding material based on high and low pressure polyethylene and polyisobutylene which contain the same amount of antimony trioxide and organic compounds containing aliphatically combined bromine are considerably less self-extinguishing.

The molding material may be prepared by mixing the propylene polymers in conventional manner with antimony trioxide and the bromine compounds, for example on rollers, kneaders or extruders. For the mixing, the bromine compounds may be added in the form of pastes or solutions, for example in acetone or chloroform, but also in the form of a concentrate in propylene polymers.

Molding material according to this invention is suitable for the production of molded articles by the usual processing methods for thermoplastics. For example sheets, boards, tubes, fibers, hollow articles, injection moldings and coatings may be prepared therewith. The molding materials are particularly suitable for use in electrical engineering and civil engineering.

Boards having a thickness of 3 mm. are pressed from the resultant molding material at 170 C. under a pressure of 200 atmospheres. Test strips having a width of 15 mm. are cut from the boards and exposed to the flame of a conventional laboratory burner. The test strips cease to burn immediately after they have been slowly withdrawn fromthe flame.

Test strips which have been prepared from 94 parts of polypropylene, 2 parts of antimony trioxide and 4 parts of hexabromodiphenyl ether or 2,4,6-tribromoaniline on the other hand continue to burn after withdrawal from the flame.

EXAMPLES 15 TO 20 Molding material based on polypropylene is made as described in Examples 1 to 14 but using other plastics; the following Table 2 gives the composition of the moldingmaterial, the columns giving the following information:

No. gives the number of the example, P gives the number of parts of polypropylene, B gives the number of parts of the bromine compound specified,

A gives the number of parts of antimony trioxide, and 0 gives the number of parts of the other plastic.

TABLE 2 No. P B A O 15 85 6 1,2,5,6-tetrabromocyclooctane 4 opgrjybigpbutylene (mol. wt. about 16 82 do low pressure polyethylene (density ,7 0.96, melt index 0.2).

17 83 5 1,2,5,G,9,10-hexabrom0cyclododecane 2 10 high pressure polyethylene (density 0.918, melt index 1.5).

18 73 .do 2 polystyrene.

19 3 1,2,5,6,9,IO-hexabromocyclododecane 2 30 copolymer oi 72% by weight of ethylshe and 28% by wt. of vinyl acetate of melt index 15.

20 74 4 1,2,5,e-tetrabromocyclooctane 2 20 copolymer of by wt. ethylene and 20% by wt. ethyl aerylate oi melt index 5.4.

The invention is further illustrated by the following examples in which parts are by weight.

EXAMPLES 1 to 14 Polypropylene having a molecular weight of about 450,000 and stabilized in conventional manner is homogeneously mixed with antimony trioxide, a compound containing aliphatically combined bromine and if desired other additives at to C. Theamounts of the components are set out in the following Table l in which the columns give the following particulars:

No. gives the number of the example,

P gives the number of parts of polypropylene,

B gives the number of parts and the bromine compound used,

A gives the number of parts of antimony trioxide, and

0 gives the number of parts of other additive.

Test strips made from this molding material as described in Examples 1 to 14 and tested under the conditions specified therein cease to burn immediately when they are slowly withdrawn from the flame of a laboratory burner.

EXAMPLE 21 TABLE 1 P B A 0 n6 3 1,2,5,6,9,IO-hexabromocyelododecano 1 nil.

94 4 1,2,3,4tetrabr0mooyclooctano 2 nil.

94 4 1,2.5,G-tetrabromocyclooctanc 2 nil.

'94 4 l-phenyl-I,2,4,5,S,9-hexabromo 2 nil.

ane.

94 4 1,2-(1ibromo4-(a,B-dibrom0ethy1- 2 nil.

cyclohcxane).

94 4 N,N,N-tris (a,6-dibrornopro- 2 nil.

pionyl)trimethylene triamine.

94 4 Methy1ene-bis-(1,Z-dibromo-l 2 nil.

methylpropionamide).

90 6 1,2-dibromo-t-(a,filibromoethyl)- 2 2 carbon black.

cyclohexane.

94 2 1,2,5,6,9,IO-hexabromocyclododec- 2 2 chlorinated polyisobutylene (chlorine ane. content 59.8% by weight).

94 3 1,2,5,fi-tetrabromoeyclooctane 2 1 tlzjhloropaaghu (chlorine content 70% Y wei t 87 9 2,3-dibromobutene-2-diol-1,4 4 nil. g

94 2 1,2,5,fi-tatrabromocyclooctane 2 2 octabromodiphenyl. I

94 2 1.2-d1bromo-4-(afl-dibromoethyb- 2 2 halogenated diphenyl containing 61% oyclohexane. by weight of bromine and 15 by weight of chlorine. 14 93 3 l.2,5,6,9,10-hexabromocyclododec- 2 2 trlbromotrichloro-diphenyl ether.

ane.

We claim:

1. A self-extinguishing thermoplastic polymer composition comprising polymers of ethylenically unsaturated monomers composed of at least 70 mol percent propylene, said polymers having a molecular weight between 100,000 and 2,000,000 and containing (A) from 0.2 to 10% by weight of antimony trioxide and (B) 1 to 13% by weight of a brominated cycloalkane containing from 6 to 12 carbon atoms in the ring, containing 45 to 93% by weight of bromine, with reference to the weight of said brominated cycloalkane, and having a boiling point above 200 C. at atmospheric pressure, the combined weight of (A) and (B) amounting to 2 to 15% by weight of said composition.

2. A composition as claimed in claim 1 wherein (B) is 1,2,5,6,9,10-hexabromocyclododecane.

3. A composition as claimed in claim 1 wherein (B) is l,2,3,4-tetrabromocyc1ooctane.

4. A composition as claimed in claim 1 wherein (B) is 1,2,5,G-tetrabrornocyclooctane.

References Cited UNITED STATES PATENTS MORRIS LIEBMAN, Primary Examiner.

J. H. DERRINGTON, Assistant Examiner.

U.S. Cl. X.R. 

1. A SELF-EXTINGUISHING THERMOPLASTIC POLYMER COMPOSITION COMPRISING POLYMERS OF ETHYLENICALLY UNSATURATED MONOMERS COMPOSED OF AT LEAST 70 MOL PERCENT PROPYLENE, SAID POLYMERS HAVING A MOLECULAR WEIGHT BETWEEN 100,000 AND 2,000,000 AND CONTAINING (A) FROM 0.2 TO 10% BY WEIGHT OF ANTIMONY TRIOXIDE AND (B) 1 TO 13% BY WEIGHT OF A BROMINATED CYCLOALKANE CONTAINING FROM 6 TO 12 CARBON ATOMS IN THE RING, CONTAINING 45 TO 93% BY WEIGHT OF BROMINE, WITH REFERENCE TO THE WEIGHT OF SAID BROMINATED CYCLOALKANE, AND HAVING A BOILING POINT ABOVE 200* C. AT ATMOSPHERIC PRESSURE, THE COMBINED WEIGHT OF (A) AND (B) AMOUNTING TO 2 TO 15% BY WEIGHT OF SAID COMPOSITION. 